CA1299461C - Laundry composition containing peroxyacid bleach and soil release agent - Google Patents
Laundry composition containing peroxyacid bleach and soil release agentInfo
- Publication number
- CA1299461C CA1299461C CA000554207A CA554207A CA1299461C CA 1299461 C CA1299461 C CA 1299461C CA 000554207 A CA000554207 A CA 000554207A CA 554207 A CA554207 A CA 554207A CA 1299461 C CA1299461 C CA 1299461C
- Authority
- CA
- Canada
- Prior art keywords
- release agent
- soil release
- polyethylene oxide
- terephthalate
- average molecular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/395—Bleaching agents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3945—Organic per-compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
Abstract
LAUNDRY COMPOSITION CONTAINING
PEROXYACID BLEACH AND SOIL RELEASE AGENT
ABSTRACT OF THE DISCLOSURE
The present invention relates to laundry cleaning compo-sitions and methods comprising a peroxyacid bleach and a soil release agent.
PEROXYACID BLEACH AND SOIL RELEASE AGENT
ABSTRACT OF THE DISCLOSURE
The present invention relates to laundry cleaning compo-sitions and methods comprising a peroxyacid bleach and a soil release agent.
Description
Case 3595M
~gg~6~L `' LAUNDt~Y COMPOSITION CONTAINING
PEROXYACID BLEACH AND SOIL RELEASE AGENT
Allen D. Clauss FIELD OF THE_INVENTION
This invention relates to laundry compositions and methods comprising bleach and soil release agents.
BACKCROUND OF THE INVENTION
.
The use of soil release agents in laundry products per se is known in the art.
Soil release agents can be mixed with other laundering components. Examples of laundry detergent compositions con-taining cellulose ether soil release agents are disclosed in U.S.
Pat. Nos. 4,000,093, C . H . Nicol and M. E . Burns, issued Dec . 28, 1976 4,100,094, M,E. Burns, issued July 11, 1978; - and 4,564,463, Secemski et al., issued Jan. 14, 1986. Examples of laundry presoak compositions and rinse additive compositions containing cellulose ether soil release agents are disclosed in U.S.
Pat. No. 4,136,038, H.J. Pracht and M.E., Burns, issued Jan. 23, 1979. Examples of laundry detergent compositions containing terephthalate ester/ethylene oxide copolymers are disclosed in U.S. Pat. Nos. 4,132,680, C.i-l. Nicol, issued Jan. 2, 2S 1979; 4,116,885, Derstadt et al., issued Sept. 26, 1978; and 4,411,831, Robinson et al., issued Oct. 25, 1983.
U.S. Pat. No. 4,132,680, supra, discloses unspecified bleaches as optional adjuncts to a detergent formulation containing a polyester soil release agent, and U.S. Pat. No. 4,210,417, McClain, issued July 1, 1980, discloses that a soil release agent may be incorporatecl into an unspecified liquid or unspecified dry bleach . U . S . Pat . No . 4,174,305, M. E. Burns, issued Nov . 13, 1979, discloses that perborate bleaches can be incorporated as dry admixes into detergent compositions containing cellulose etller soil release agents. U.S. Pat. No. 4,116,885, supra, discloses .~
6~
that bleaching agents can be incorporated into detergent formu-lations containing polyester soil release agents, specific examples given were chlorinated trisodium phosphate, and sodium and potassium salts of dichloroisocyanuric acid.
In ncne of the above disclosures was there an indication of superior or synergistic performance benefits in using any type of bleach in combination with a soil release agent.
Organic peroxyacid bleaches are known; but it is believed that heretofore they have not been known to be used in combi-nation with soil release agents.
OBJECTS OF THE INVENTION
It is an object of the present invention to provide an improved laundry cleaning product which provides superior -i5 bleaching and cleaning of hydrophobic soils on synthetic fabrics and synthetic natural blend fabrics by use of a combination of peroxyacid bleaches and a soil release agent.
It is a further object of the present invention to provide laundry cleaning formulations which employ a peroxyacid bleach and a soil release agent to achieve performance beyond that possible with a comparable amount of either the peroxyacid or the soil release agent alone.
It is yet another object of this invention to provide a more cost-effective peroxyacid bleach containing laundry product in which part of the expensive peroxyacid bleach is replaced by a less costly soil release agent and yet providing a product having equal or superior overall bleaching/cleaning performarlce to one with higher levels of bleach.
These and other objects of this invention will become appar-ent in the light of the following disclosure.
SUMMARY OF T~IE INVENTION
. .
The present invention relates to laundry cleaning compo-sitions and methods comprising a peroxyacicl bleach and a soil 3s release agent.
~2~
DET~ILED_DESCRIPTION OF THE INVENTION
The present invention provides an unexpectedly superior laundry cleaning composition comprising effective amounts of a peroxyacid bleach and a soil release agent. The peroxyacid and S the soil release agent are preferably present at a ratio of weight of available oxygen to weight of soil release agent of from about 10:1 to about 1:10, more preferably from about 5:1 to about 1:5, and presently most preferably from about 2 :1 to about 1: 2 . The present invention can be incorporated into a fully formulated, stand alone product, or it can be formulated as an additive to be used in combination with a laundry detergent. It is preferably a dry composition, but can be in whole or in part a liquid or paste.
The peroxyacid can be a preformed peroxyacid or it can be a combination of an inorganic persalt (e.g., sodium perborate) l 5 and an organic peroxyacid precursor which is converted to a peroxyacid when the combination of persalt and presursor is dissolved in water. The organic peroxyacid precursors are often referred to in the art as bleach activators.
Examples of suitable organic peroxyacids are disclosed in U . S . Pat . No. 4, 374, 035, F. P. Bossu, issued Feb . 15, 1983 .
Examples of compositions suitable for laundry bleaching which contain preferred activated perborate bleaches are disclosed in U.S. Pat. No. 4,412,934, Chung and Spadini, issued Nov. 1, 1 983 .
Th~ preferred organic peroxyacid is selected from the fol lowing:
O O
"
H - O - O - C - R l - Y H - O - O - C - CH - R - Y
X
ll l H - O - O - Rl - C - N - R - Y
ll l ll H - O - O - C - R~ - N - C - R2 ~ Y
wherein Rl and R2 are alkylene groups containing from l to about 20 carbon atoms or phenylene groups, R3 is hydrogen or an alkyl, aryl, or alkaryl group containing from about l to about 10 carbon atoms, and X and Y are hydrogen, halogen, alkyl, aryl, or any group which provides an anionic moiety in aqueous solu-tion. Such X and Y groups can include, for example, O O O
ll ll ll - C - OM - C - O - O - M - S - O - M
where M is hyclrogen or a water-soluble salt-forming cation.
Mixtures of peroxyaclds can be useci.
Specl flc examples of preferred peroxyacids for this invention include dlperoxydodecanedioic acid (DPDA), nonylamlde of per-oxysuccinlc acid (NAPSA), decyldiperoxysuccinic acid (DDPSA).
For the purpose of ~his invention, the peroxyacid is preferably incorporated into a soluble granule according to the method described in U.S. Pat. No. 4,374,035~ supra . T~ perox~-acid ~leach is use~ at a level which provides an amount of available oxygen (AvO) from about 0.10% to about 10%, preferably from about 0.5~ to about 5~, and most preferably from about 1% to about 4~. A preferred bleach gran-ule comprises 1% to 50% of an exotherm control agent ~e.g., boric acid); 196 t~ 25~ of a peroxyacid compatible surfactant (e.g., C13LAS); 0.1% to 10% of one or more chelant stabili2ers (e.g., sodium pyrophosphates); and 10% to 50~ of a water-soluble pro-cessing salt (e.g., Na2SO~
Alternatively, the composition may contain a suitable organic precursor which generates one of the above peroxyacids when reacted with alkaline hydrogen peroxide in aqueous solution. The source of hydrogen peroxiçie can be any inorganic peroxygen compound which dissolves in aqueous solution to generate hydro-gen peroxide, e.g., sodium perborate (monohydrate and tetra-hydrate) and sodium percarbonate.
These compositions comprise:
(a) a peroxygen bleaching compound capable of yielding hydrogen peroxide in an aqueous solution; and (b) a bleach activator having the general formula:
O
ll R - C - L
wherein R Is an alkyl group containlng from about 5 to about 18 carbon atoms wherein the longest linear alkyl chain extending frorn and including the carbonyl carbon contains from about 6 to about 10 carbon atoms and L is a leaving group, the conjugate acid of which has a PKa In ~he range of from about 6 to about 13.
4~
Preferred compositions comprise an effective amount of soil release agent and peroxyacid bleach precursor and paroxygen compound to work in the wash solution. The peroxygen com-pound to soil release agent ratios are preferably 30:1 to 1:10;
15:1 to 1 5 and 3:1 to 1:2 on an AvO weight to sbil release agent weight basis.
Any compatible soil release agent can be used in the present invention. For example, two general classes of nonionic water-soluble or water-dispersible polymers, cellulose ethers, and terephthalate ester/ethylene oxide copolymers are known to pro-vide soil release benefits. While not being bound to any theory, it is believed that they do this by adsorbing onto fabrics, par-ticularly synthetic fabrics such as polyester, such that stains, particularly greasy stains, subsequently transferred to the fabric are more easily removed in the next wash cycle.
The preferred soil release agent is selected from the following:
A. alkyl and hydroxyalkyl ethers of cellulose containing from one to four carbon atoms in the alkyl or hydroxyalkyl moiety and having a molar degree of substitution of about 1 . 5 to about 2 . 7 and a number average molecular weight of about 2,000 to 100,000;
B, polyrners comprising ethylene terephthalate and poly-ethylene oxide terephthalate at mole ratio from about 1:10 to 10:1, said polyethylene oxide terephthalate containing polyethylene oxide uni ts with a number average molecular weight from about S00 to about 10,000, and said soll release agent having a number average molecular weight of about 1,000 to 100,000;
C. polymers comprlsing propylene terephtalate and poly-ethylene oxide terephthalate at a mole ratio from about 1 :10 to about 10:1, said polyethylene oxide tere-phthalate containing polyethylene oxide units with a number average molecular weight from about S00 to about 10,000, and said soil release agent having a number average molecular weight of about 1,000 to 100,000;
~g~
D. polymers comprising ethylene terephthalate and/or propylene terephthalate in any ratio and polyethylene oxide and/or polypropylene oxide in any ratio such that the mole ratio of ethylene terephthalate plus propylene terephthalate to polyethylene oxide plus propylene oxide is from about 1 :10 to about 10:1, said polyethylene oxide units and said polypropylene oxide units each having a number average molecular weig~it from about 259 to about 10,ûO0, and said soil release agent having a number average molecular weight of about 1,000 to about 100, 000 .
Any combination of the a~ove soil release agents can be used.
It is an essential aspect of the present invention that the soil release agent be formulated and delivered in a manner that provides adsorption of this active to hydrophobic synthetic fabrics during the laundry process. Ideally the polymer is de-livered in such a way and at levels which provide essentially the maximum soil release effect after a single wash-rinse-dry cycle.
That is, essentially the full soil release advantage can be observed in the second washing of any particular garment.
It is intended that the scope of the present invention en-compasses products and laundering methods in which the bleach component is released entirely in the wash and the soil release agent component is released entirely or partially in: the wash cycle, ~n the rinse cycle, or in the drying cycie, including partial dellvery of the soil release agent in each of the different cyctes .
Wash Cycle -When most or all of the soll release agent Is delivered in the wash cycle, the efficiency of deposltion on fabric and consequent soil release performance is dependent on the selection of soil release agent, c!etergent builder anci surfactant actives. U.S.
Pat. No. l~,000,093, ~E~ iscloses cellulose-based soil release agents suitable for use in ~.
combination with detergent compositions. The preferred surfac-tants are the C1 0-Cl 3 alkyl sulfate surfactants which are sub stantially free from interfering amounts of longer-chain length alkyl sulfates. U.S. Pat. No. 4,116,8B5, supra, discloses polyester/polyether soil release agents used with only limited amounts of inc~mpatible anionic surfactants.
In a different approach, U.S. Pat. No. 4,020,015, G. Bevan, issued Apr. 26, l977, teaches that a variety of soil release agents show enhanced performance in dry granular detergents when the soil release agent Is incorporated as a separate granular extrudate consistlng of the soil release agent and an extrudable organic carrier. The latter approach has been found to be Llseful for formulating a soil release agent for the current invention. For example methyl-cellulose soil release agents such as those sold by Dow Chemical Co. under the trade name MethocelR can be blended in a 1:1 ratio with polyethylene glycol le.g., Carbowax PEG 3350) and the resultant blend extruded on a radial extruder and ground to the desired particle size. The resultant granular extrudates are rapidly soluble and provide excellent soil release performance when delivered to the wash cycle with a variety of different detergent formulations.
Rinse Cycle Dellvery Enhanced soil release performance can be achieved for a variety of soil release agents by delivering them into the r5nse cycle Instead of the wash cycle. In particular, polyester/poly-ether soll release agents which are hlghly sensltive to inter-ference by anionic surfactants In the wash can be used much more effectively with anlonic detergents by rinse cycle delivery.
Examples of su5table soil relea~e agents for use in the rinse cycle in the context of the present invention include ethylenetereph-thalate/ethyleneoxide copolymers sold by DuPont under the Zelcon trade name and by ICI under the MileaseRtrade name. These 3~ materials can be delivered to the rinse cycle as aqueous ~' 6~
dispersions or as rapidty dispersing granules or powders. An example of the latter form can be made by taking a suitable Zelcon material in the pure solid form, heating it to its softening point, and blending it with an equal mass of urea such that the urea and polymer are uniformly distributed. The resultant mass is cooled to a harci solid and ground to the desired granule size.
The resultant granules disperse rapidly in a coki water rinse solution and provide excellent soil release performance.
In cases where it is particularly desirable to add the soil release agent in the rinse cycle, the polymer as an aqueous slurry or incorporated into granules as described can be manually added to the rinse cycle following a wash cycle in which one of the preferred peroxyacid bleaches is used. Preferably, however, the soil release agent component is incorporated into a single product also containing the peroxyacid bleach in such a way that the bleach is released in the wash cycle and the soil release agent is released in the rinse cycle of an automatic washing machine.
There are several laundry product designs which can be used to effect such a sequential release delivery of actives. For example, U.S. Pat. No. 4,108,600, Wong, issued Aug. 22, 1978, describes fabric condit.ioning articles which release an electrolyte or pH control agent in the wash, the effect of which is to render insoluble in the wash a coating agent surrounding and protecting the active (i.e., soil release agent of the present invention) to be delivered In the rinse cycle. In a preferred embodiment the article consists of a porous outer pouch of spunbonded polyester whlch contains sodium borate and an inner nonporous film pouch of a polyvinyl alcohol which is ren-dered insoluble by the sodium borate in the wash solution and contalns wlthin It soll release agent to be delivered in the rinse cycle. For the purpose of the present Invention, the article is made to contain peroxyacid bleach and, optionally, detergent in additlon to sodium borate in the outer pouch, and soil release agent granules in the inner pouch. A product made in such a way releases the peroxyacid and detergent components at the lt 4~
- 1~
beginning of the wash cycle and releases the soil release agent component in the rinse cycle.
Other patents, which describe potentially useful product designs for automatic release of actives in the rinse cycle include:
Canadian Pat. No. 1,133,712, Bristol-Myers Co., issued Oct. 19, 1982; U.S. Pat. Nos, 4,304,562, Bolan et al., issued Dec. 8, 1981; and 4,588,~80, C;inn et al., issued May 13, 1986.
O~tionals If the present invention is used in combination with a pouch, a bag, or the like, preferred pouch substrates are set out in the examples. Suitable substrates are also taught in U.S. Pat. No. 4,113,630, supra, U.S. Pat.
No. 4,108,600 suPra, Canadian Pat. No. 1,245,533; and Canadian Pat. 1,245,943. It is advantageous to include a substrate which contains or supports the active ingredients in a premeasured, single use amount and releases them at the desired point in the wash and/or rinse cycle. The substrate may also be used to separate or compartmentalize incompatible ingredients until they are released into the wash solution. As described above, a specially designed substrate may be particularly useful to effect a sequenced delivery in which the detergent and bleach ingredients are released in the wash cycle and the soil release agent is released in the late wash and/or rinse cycle. The substrate can take almost any physical form including pouches, sheets, webs, sponges, cups, etc. It may consist of nondissolving, partially dissolving or fully dissolving material, or combinations thereof. An example of a particularly useful substrate or the present invention is a two-ply multi-pouched laminated artiole disclosed in Canadian Pat. No. 1,245,943, W.T. Bedenk and K.L. Harden.
Th2 present invention Is preferably used as part of a fully 35 formulated 5tand-alone detergent product wherein appropriate ~ detergent components are present and released along with the ~z~
peroxyacid bleach and soil release agent. Useful detergent compositions for use with this invention can include essentially any typical laundry detergent containing one or more types of organic surfactant along with detergency adjunct mat~rials. The organic ~urfactant is selected from the group consisting of anionic, nonionic, ampholytic and zwitterionic surfactants, and mixtures thereof. U.S. Pat. 3,664,961, Norris, issued May 23, 1972, describes at Col~ 1, line 68, to Col. 9, line 3, suitable surfactants useful herein. The anionic and nonionic surfactants are preferred. Nonlimiting examples of adjunctmaterials which can be used in the detergent composition include soil suspending agents, perfumes, optical ~leaches, processing aids, alkalinity sources and enzymes. Nonlimiting examples of powdered detergentmaterials suitable for use with the present invention are disclosed in U.S. Pat. No, 4,404,128, B.J. Anderson, issued Sept. 13, 1983.
Fabric softeners can also be used in combination with the components of the present invention. A pre-ferred softener is a particle formulated to survive (i.e., not dissolve in) the wash and rinse cycle, and melt and become distributed evenly on the fabric in the dryer cycle. The softener particle composition wash water survival should be at least 25%, preferably at least 40%
by weight. Numerous examples of softener/antistat compositions which function in this manner are taught in the literature, e.g., U.S. Pat. Nos. 4,113,630, Hagner et al, issued Sept. 12, 1978, and 4,108,600, supra.
A preferred fabric sotener (core) particle has the following formula:
I n~ red ient W
Ditallowdimethylammonium methylsul~ate (DTDMAMS) 4204 Sorbitan monostearate 21. 3 Cetyl alcohol 21 . 3 Bentonite clay 12 . 0 Perfume 3, 0 Total 100. 0 10The softener core particles are coated with stearyl alcohol in an amount such that the stearyl alcohol comprises 11% of the total particle composition (i.e., core plus coatingl.
The coated particles can be used "as is" as softener par-ticles with or without detergent granules. They can be over-15coated with a hard shell of ethyl cellulose, e.g., Ethocel Std. Ll, (Dow Chemical Co., Midland, Michigan 4B640). The amount of ethyl cellulose solids overcoated onto the particles is about 3% by weight of the total particle weight. The softener particles are sized through 12 on 30 Mesh U. S. Standard screens.
Deter~enttSoftener Composition A granular detergent/softener composition is prepared bymixing 3 parts of the above ethyl cellulose overcoated softener partlcles with 97 parts of the following granular detergent com-25 position.
Ing edient Wt.%
Sodium C13 linear alkylbenzene sul~onate 16.5 Sodium C1 4-C1 5 linear fatty alcohol sulfate 16 . 5 Sodium sulfate 23 . 8 Sodium silicate 9.2 Polyethylene glycol o. g Polyacrylic acid 1.3 Sodium tripolyphosphate13 . 7 Sodium carbonate 4.8 Methyl cellulose 3.6 Optical brightener 1.3 Protease enzyme 1.6 Moisture and miscellaneous 6.8 'rota I1 oo . o B leach / Softener Composition A granular bleach/softener composition is prepared by mixing 4 parts of either the above stearly alcohol coated softener par-ticles or the above ethyl cellulose overcoated softener particles with 96 parts of the following granular bleach composition.
I n~ redient Wt .
r)iperoxydodecanedloic acid 24.0 Dodecanedioic acid 2.9 Sodium C13 linear alkylbenzene su I fonate 5 . 5 Boric acid 27.7 Sodium sulfate 39.7 Miscellaneous 0. 2 Total100.0 The present invention will be further understood by the following nonlimiting examples.
E XAM PLE
A granule containing methylcellulose soil release agent which diss~lves rapidly under laundry wash cycle conditions is made according to the following procedure:
Methylcellulose powder (182 kg ~400 Ibs.) oF Dow Methocel A-15LV Premium Grade) and polyethylene glycol (182 kg (400 Ibs. ) of Union Carbide Carbowax PEG 3350) are blended in a rotating drum mixer for 5 minutes. The blended material is then divided into four 200 L (55 gal. ) fiber drums which are stored at 49C (120F) for 36 hours . The powder blend is then fed by hand into a radial extruder (Fuji Pandal Model EXDCS-100). The temperature of the material entering the extruder is ca 38C
(100F). The resulting extrudate is recycled once through the extruder. After allowing the extrudate to cool to room tempera-ture it is run through a Fitzmill Model DA506 using a U.S. No.
14 mesh screen . The resultant material is sieved on a Rotex uCing a U . S. No. 48 mesh screen to remove fine particles.
EXAMPLE l l A nonwoven fabric is coated with soil release agent according to the following procedure:
450 ml of distilled water are added to a 2000 ml stainless steel beaker and heated to 70C (158F) . 80 grams of Dow Chemical s Methocel A-15LV Premium Crade methylcellulose are slowly added to the water under good agitation conditions (a vortex was present). After the methylcellulose is well dispersed the agitation is reduced to prevent aeration. 438 grams of 20C
(68F) water are then added to the dispersion. Propylene ylycol (32.09) is then added. The beaker is then placed in an Ice bath and agitation contlnued until product became clear (an indication that the methylcellulose was dissolved). An 11.4 cm x 28 cm (4.5 in. x 11 in. ) sheet of DuPont Reemay 2420 (a spunbonded 63 g/m2 4 denier polyester fabric) was immersed in the methylcel-lulose solution. The saturated fabric was then run through an Atlas Electric Devices Co. Iaboratory wringer (Model LW-1) set at approximately 50 kg (110 Ibs. ) force. The wrung-out fabric is ~g~46~
then line dried in a low humidity environment for 24 hours.The substrate is coated with about 0.75 9 (0.028 oz.) of solid coatirlg.
EXAMPLE l l I
A bleach granule having the composition detailed below is prepared usiny the procedure described in Example I of U . S.
Pat . No. 4, 374, 035, supra .
I ng red ient Wt . %
Diperoxydodecanedioic acid24.0 Dodecanedioic acid 2.9 Sodium C13 linear alkylbenzene sul fonate 5 . 5 Boric acid 27.7 Sodium sulfate 39,7 Miscellaneous 0. 2 Total100. 0 - .
...
~g~
E)(AMPLE IV
The following granular detergent composition is prepared.
Base Granules Grams Final Composition Weight ~ Per Use Sodium C13 linear alkyl-benzene sulfonate 22.1 5.110 Sodium C1LI_15 alkyl sulfate22.1 5.110 Sodium silicate (1.6 ratio) 13.7 3.172 Sodium sulfate 32.2 7.455 Polyethylene glycol (MW = 8000) 1.5 0.340 Sodium polyacrylate lMW = 4500) 2.0 0.453 C12_13 alcohol poly-ethoxylate (6) 3.0 0.680 Sodium diethylenetriamine pentaacetate 1.5 0.34û
Moisture 2.0 0.462 23.12 Preblend Base granules 23.122 Sodium tripolyphosphate hexahydrate (powdered) 20.576 43.698 ~3i9~
EXAMPLE IV - Contd.
Admix Preblend 43. 698 Sodium tripolyphosphate (STP) hexahydrate (granular~ 19, 429 Dye 003 Brightener 0. 613 Suds suppressor prill comprising dimethylsilicone, silica, sodium tripolyphosphate and polyethylene glycol (MW = 8000) 1.703 Base Granules Crams Final Composition Weight %Per Use Protease 2 . 044 Sodium carbonate 4, 000 71, 490 Spray-On Admix 71.490 Mineral oil 0. 710 72.200 The base granules are produced by spray-drying an aqueous crutcher mix of the components on a ten foot tower using a crutcher temperature of 200F, a size 3-l/2 nozzle to make fine granules, and silicone deaeratants. I f a second drying stage on a continuous fluid bed is used to reduce moisture to 2%.
3946~
The base granules are then admixed with powdered STP
hexahydrate to form the preblend. The preblend is compacted at 50 psig roll pressure on a 4 in. by 10 in. chilsonator, and screened to select a -14(1168 microns)/+65(208 microns) particle ske cut (Tyler mesh). Oversized particles are collected and granulated on a Fitzmill, Model DA506 (The Fitzpatrick Company, Elmhurs~, Illinois 60126), using a 14 mesh screen and low rpm's.
This is screened to select a -20(833 microns)/+48(295 microns) particle size cut. Both materials are dedusted by blowing off fines in a fluid bed dryer using ambient air.
The admix is prepared as a 400 pound batch in a drum mixer. Carbonate, granular STP (with dye sprayed-on), bright-ener, enzymes, and suds suppressor prills are blended with the compacted mainstream product cut and regranulated overs at a ratio of mainstream product cut to overs of about 7 to 1. Mineral oil is sprayed on the final admix in 30 to 40 pound batches at a 19~ level using a Forberg Mixer, EXAMPLE V
A preferred mode multipouched laundry cleaning article consisting of the soil release agent coated nonwoven substrate of Example ll containing detergent tEx. IV) and bleach granular lEx. Ill) compositions is made using the following procedure. A
11.4 cm x 28 cm (4.5 in~ x 11 in.) sheet of DuPont Reemay 242û
2S la spunbonded, 63 g/rn2, 4 denier polyester fabric) Is embossecl or stretched to form a single roll of 6 cells simllar to the pattern shown in Flgs. 7 and 8 of U.S. Pat. No. 4,571,924, A.S. Bahrani, issued Feb. 25, 198fi. The six cups are em~ossed to a depth of approximately 1.0 cm (0.4 in.), and heat set. Each cup is approximately 3.6 cm. (1.4 in . ) wide and approximately 9 . 8 cm . ( 3.8 in . ) in length, each with about 30 cc capacity. Two cups are each filled with approximately 14 grams (0. 50 oz . ) of the granular bleach com-position described in Example l l l . Each of the eight cups is filled with approximately 18 grams 10.64 oz.) of the granular detergent composition described in Example IV. A topsheet ply of ~12~
the same dimensions and material as used for the embossed sheet is then attached to the filled, embossed ply by heat sealing with a sheet of polyethylene patterned to correspond to the rims of embossed ply. The nDnwoven substrate is coated with methyl-cellulose soil release agent according to Example l l such that the total level of methylcellulose in the article is about 1. lg. The AvO to soil release agent ratio for this article is about 1:1.2~ and the product delivers about 12 ppm AvO and 16 ppm of soil release agent in a 68 liter wash solution.
EXAMPLE Vl A multipouched laundry cleaning article is made according to Example V with the addition of 0.54 gram of the soil release agent granules described in Example I added to each of the four deter-gent pouches with a noncoated substrate. The total amount of soil release agent active is about 1.1 grams, thus the AvO to soil release agent ratio for this article is about 1:1.3.
.~ ,
~gg~6~L `' LAUNDt~Y COMPOSITION CONTAINING
PEROXYACID BLEACH AND SOIL RELEASE AGENT
Allen D. Clauss FIELD OF THE_INVENTION
This invention relates to laundry compositions and methods comprising bleach and soil release agents.
BACKCROUND OF THE INVENTION
.
The use of soil release agents in laundry products per se is known in the art.
Soil release agents can be mixed with other laundering components. Examples of laundry detergent compositions con-taining cellulose ether soil release agents are disclosed in U.S.
Pat. Nos. 4,000,093, C . H . Nicol and M. E . Burns, issued Dec . 28, 1976 4,100,094, M,E. Burns, issued July 11, 1978; - and 4,564,463, Secemski et al., issued Jan. 14, 1986. Examples of laundry presoak compositions and rinse additive compositions containing cellulose ether soil release agents are disclosed in U.S.
Pat. No. 4,136,038, H.J. Pracht and M.E., Burns, issued Jan. 23, 1979. Examples of laundry detergent compositions containing terephthalate ester/ethylene oxide copolymers are disclosed in U.S. Pat. Nos. 4,132,680, C.i-l. Nicol, issued Jan. 2, 2S 1979; 4,116,885, Derstadt et al., issued Sept. 26, 1978; and 4,411,831, Robinson et al., issued Oct. 25, 1983.
U.S. Pat. No. 4,132,680, supra, discloses unspecified bleaches as optional adjuncts to a detergent formulation containing a polyester soil release agent, and U.S. Pat. No. 4,210,417, McClain, issued July 1, 1980, discloses that a soil release agent may be incorporatecl into an unspecified liquid or unspecified dry bleach . U . S . Pat . No . 4,174,305, M. E. Burns, issued Nov . 13, 1979, discloses that perborate bleaches can be incorporated as dry admixes into detergent compositions containing cellulose etller soil release agents. U.S. Pat. No. 4,116,885, supra, discloses .~
6~
that bleaching agents can be incorporated into detergent formu-lations containing polyester soil release agents, specific examples given were chlorinated trisodium phosphate, and sodium and potassium salts of dichloroisocyanuric acid.
In ncne of the above disclosures was there an indication of superior or synergistic performance benefits in using any type of bleach in combination with a soil release agent.
Organic peroxyacid bleaches are known; but it is believed that heretofore they have not been known to be used in combi-nation with soil release agents.
OBJECTS OF THE INVENTION
It is an object of the present invention to provide an improved laundry cleaning product which provides superior -i5 bleaching and cleaning of hydrophobic soils on synthetic fabrics and synthetic natural blend fabrics by use of a combination of peroxyacid bleaches and a soil release agent.
It is a further object of the present invention to provide laundry cleaning formulations which employ a peroxyacid bleach and a soil release agent to achieve performance beyond that possible with a comparable amount of either the peroxyacid or the soil release agent alone.
It is yet another object of this invention to provide a more cost-effective peroxyacid bleach containing laundry product in which part of the expensive peroxyacid bleach is replaced by a less costly soil release agent and yet providing a product having equal or superior overall bleaching/cleaning performarlce to one with higher levels of bleach.
These and other objects of this invention will become appar-ent in the light of the following disclosure.
SUMMARY OF T~IE INVENTION
. .
The present invention relates to laundry cleaning compo-sitions and methods comprising a peroxyacicl bleach and a soil 3s release agent.
~2~
DET~ILED_DESCRIPTION OF THE INVENTION
The present invention provides an unexpectedly superior laundry cleaning composition comprising effective amounts of a peroxyacid bleach and a soil release agent. The peroxyacid and S the soil release agent are preferably present at a ratio of weight of available oxygen to weight of soil release agent of from about 10:1 to about 1:10, more preferably from about 5:1 to about 1:5, and presently most preferably from about 2 :1 to about 1: 2 . The present invention can be incorporated into a fully formulated, stand alone product, or it can be formulated as an additive to be used in combination with a laundry detergent. It is preferably a dry composition, but can be in whole or in part a liquid or paste.
The peroxyacid can be a preformed peroxyacid or it can be a combination of an inorganic persalt (e.g., sodium perborate) l 5 and an organic peroxyacid precursor which is converted to a peroxyacid when the combination of persalt and presursor is dissolved in water. The organic peroxyacid precursors are often referred to in the art as bleach activators.
Examples of suitable organic peroxyacids are disclosed in U . S . Pat . No. 4, 374, 035, F. P. Bossu, issued Feb . 15, 1983 .
Examples of compositions suitable for laundry bleaching which contain preferred activated perborate bleaches are disclosed in U.S. Pat. No. 4,412,934, Chung and Spadini, issued Nov. 1, 1 983 .
Th~ preferred organic peroxyacid is selected from the fol lowing:
O O
"
H - O - O - C - R l - Y H - O - O - C - CH - R - Y
X
ll l H - O - O - Rl - C - N - R - Y
ll l ll H - O - O - C - R~ - N - C - R2 ~ Y
wherein Rl and R2 are alkylene groups containing from l to about 20 carbon atoms or phenylene groups, R3 is hydrogen or an alkyl, aryl, or alkaryl group containing from about l to about 10 carbon atoms, and X and Y are hydrogen, halogen, alkyl, aryl, or any group which provides an anionic moiety in aqueous solu-tion. Such X and Y groups can include, for example, O O O
ll ll ll - C - OM - C - O - O - M - S - O - M
where M is hyclrogen or a water-soluble salt-forming cation.
Mixtures of peroxyaclds can be useci.
Specl flc examples of preferred peroxyacids for this invention include dlperoxydodecanedioic acid (DPDA), nonylamlde of per-oxysuccinlc acid (NAPSA), decyldiperoxysuccinic acid (DDPSA).
For the purpose of ~his invention, the peroxyacid is preferably incorporated into a soluble granule according to the method described in U.S. Pat. No. 4,374,035~ supra . T~ perox~-acid ~leach is use~ at a level which provides an amount of available oxygen (AvO) from about 0.10% to about 10%, preferably from about 0.5~ to about 5~, and most preferably from about 1% to about 4~. A preferred bleach gran-ule comprises 1% to 50% of an exotherm control agent ~e.g., boric acid); 196 t~ 25~ of a peroxyacid compatible surfactant (e.g., C13LAS); 0.1% to 10% of one or more chelant stabili2ers (e.g., sodium pyrophosphates); and 10% to 50~ of a water-soluble pro-cessing salt (e.g., Na2SO~
Alternatively, the composition may contain a suitable organic precursor which generates one of the above peroxyacids when reacted with alkaline hydrogen peroxide in aqueous solution. The source of hydrogen peroxiçie can be any inorganic peroxygen compound which dissolves in aqueous solution to generate hydro-gen peroxide, e.g., sodium perborate (monohydrate and tetra-hydrate) and sodium percarbonate.
These compositions comprise:
(a) a peroxygen bleaching compound capable of yielding hydrogen peroxide in an aqueous solution; and (b) a bleach activator having the general formula:
O
ll R - C - L
wherein R Is an alkyl group containlng from about 5 to about 18 carbon atoms wherein the longest linear alkyl chain extending frorn and including the carbonyl carbon contains from about 6 to about 10 carbon atoms and L is a leaving group, the conjugate acid of which has a PKa In ~he range of from about 6 to about 13.
4~
Preferred compositions comprise an effective amount of soil release agent and peroxyacid bleach precursor and paroxygen compound to work in the wash solution. The peroxygen com-pound to soil release agent ratios are preferably 30:1 to 1:10;
15:1 to 1 5 and 3:1 to 1:2 on an AvO weight to sbil release agent weight basis.
Any compatible soil release agent can be used in the present invention. For example, two general classes of nonionic water-soluble or water-dispersible polymers, cellulose ethers, and terephthalate ester/ethylene oxide copolymers are known to pro-vide soil release benefits. While not being bound to any theory, it is believed that they do this by adsorbing onto fabrics, par-ticularly synthetic fabrics such as polyester, such that stains, particularly greasy stains, subsequently transferred to the fabric are more easily removed in the next wash cycle.
The preferred soil release agent is selected from the following:
A. alkyl and hydroxyalkyl ethers of cellulose containing from one to four carbon atoms in the alkyl or hydroxyalkyl moiety and having a molar degree of substitution of about 1 . 5 to about 2 . 7 and a number average molecular weight of about 2,000 to 100,000;
B, polyrners comprising ethylene terephthalate and poly-ethylene oxide terephthalate at mole ratio from about 1:10 to 10:1, said polyethylene oxide terephthalate containing polyethylene oxide uni ts with a number average molecular weight from about S00 to about 10,000, and said soll release agent having a number average molecular weight of about 1,000 to 100,000;
C. polymers comprlsing propylene terephtalate and poly-ethylene oxide terephthalate at a mole ratio from about 1 :10 to about 10:1, said polyethylene oxide tere-phthalate containing polyethylene oxide units with a number average molecular weight from about S00 to about 10,000, and said soil release agent having a number average molecular weight of about 1,000 to 100,000;
~g~
D. polymers comprising ethylene terephthalate and/or propylene terephthalate in any ratio and polyethylene oxide and/or polypropylene oxide in any ratio such that the mole ratio of ethylene terephthalate plus propylene terephthalate to polyethylene oxide plus propylene oxide is from about 1 :10 to about 10:1, said polyethylene oxide units and said polypropylene oxide units each having a number average molecular weig~it from about 259 to about 10,ûO0, and said soil release agent having a number average molecular weight of about 1,000 to about 100, 000 .
Any combination of the a~ove soil release agents can be used.
It is an essential aspect of the present invention that the soil release agent be formulated and delivered in a manner that provides adsorption of this active to hydrophobic synthetic fabrics during the laundry process. Ideally the polymer is de-livered in such a way and at levels which provide essentially the maximum soil release effect after a single wash-rinse-dry cycle.
That is, essentially the full soil release advantage can be observed in the second washing of any particular garment.
It is intended that the scope of the present invention en-compasses products and laundering methods in which the bleach component is released entirely in the wash and the soil release agent component is released entirely or partially in: the wash cycle, ~n the rinse cycle, or in the drying cycie, including partial dellvery of the soil release agent in each of the different cyctes .
Wash Cycle -When most or all of the soll release agent Is delivered in the wash cycle, the efficiency of deposltion on fabric and consequent soil release performance is dependent on the selection of soil release agent, c!etergent builder anci surfactant actives. U.S.
Pat. No. l~,000,093, ~E~ iscloses cellulose-based soil release agents suitable for use in ~.
combination with detergent compositions. The preferred surfac-tants are the C1 0-Cl 3 alkyl sulfate surfactants which are sub stantially free from interfering amounts of longer-chain length alkyl sulfates. U.S. Pat. No. 4,116,8B5, supra, discloses polyester/polyether soil release agents used with only limited amounts of inc~mpatible anionic surfactants.
In a different approach, U.S. Pat. No. 4,020,015, G. Bevan, issued Apr. 26, l977, teaches that a variety of soil release agents show enhanced performance in dry granular detergents when the soil release agent Is incorporated as a separate granular extrudate consistlng of the soil release agent and an extrudable organic carrier. The latter approach has been found to be Llseful for formulating a soil release agent for the current invention. For example methyl-cellulose soil release agents such as those sold by Dow Chemical Co. under the trade name MethocelR can be blended in a 1:1 ratio with polyethylene glycol le.g., Carbowax PEG 3350) and the resultant blend extruded on a radial extruder and ground to the desired particle size. The resultant granular extrudates are rapidly soluble and provide excellent soil release performance when delivered to the wash cycle with a variety of different detergent formulations.
Rinse Cycle Dellvery Enhanced soil release performance can be achieved for a variety of soil release agents by delivering them into the r5nse cycle Instead of the wash cycle. In particular, polyester/poly-ether soll release agents which are hlghly sensltive to inter-ference by anionic surfactants In the wash can be used much more effectively with anlonic detergents by rinse cycle delivery.
Examples of su5table soil relea~e agents for use in the rinse cycle in the context of the present invention include ethylenetereph-thalate/ethyleneoxide copolymers sold by DuPont under the Zelcon trade name and by ICI under the MileaseRtrade name. These 3~ materials can be delivered to the rinse cycle as aqueous ~' 6~
dispersions or as rapidty dispersing granules or powders. An example of the latter form can be made by taking a suitable Zelcon material in the pure solid form, heating it to its softening point, and blending it with an equal mass of urea such that the urea and polymer are uniformly distributed. The resultant mass is cooled to a harci solid and ground to the desired granule size.
The resultant granules disperse rapidly in a coki water rinse solution and provide excellent soil release performance.
In cases where it is particularly desirable to add the soil release agent in the rinse cycle, the polymer as an aqueous slurry or incorporated into granules as described can be manually added to the rinse cycle following a wash cycle in which one of the preferred peroxyacid bleaches is used. Preferably, however, the soil release agent component is incorporated into a single product also containing the peroxyacid bleach in such a way that the bleach is released in the wash cycle and the soil release agent is released in the rinse cycle of an automatic washing machine.
There are several laundry product designs which can be used to effect such a sequential release delivery of actives. For example, U.S. Pat. No. 4,108,600, Wong, issued Aug. 22, 1978, describes fabric condit.ioning articles which release an electrolyte or pH control agent in the wash, the effect of which is to render insoluble in the wash a coating agent surrounding and protecting the active (i.e., soil release agent of the present invention) to be delivered In the rinse cycle. In a preferred embodiment the article consists of a porous outer pouch of spunbonded polyester whlch contains sodium borate and an inner nonporous film pouch of a polyvinyl alcohol which is ren-dered insoluble by the sodium borate in the wash solution and contalns wlthin It soll release agent to be delivered in the rinse cycle. For the purpose of the present Invention, the article is made to contain peroxyacid bleach and, optionally, detergent in additlon to sodium borate in the outer pouch, and soil release agent granules in the inner pouch. A product made in such a way releases the peroxyacid and detergent components at the lt 4~
- 1~
beginning of the wash cycle and releases the soil release agent component in the rinse cycle.
Other patents, which describe potentially useful product designs for automatic release of actives in the rinse cycle include:
Canadian Pat. No. 1,133,712, Bristol-Myers Co., issued Oct. 19, 1982; U.S. Pat. Nos, 4,304,562, Bolan et al., issued Dec. 8, 1981; and 4,588,~80, C;inn et al., issued May 13, 1986.
O~tionals If the present invention is used in combination with a pouch, a bag, or the like, preferred pouch substrates are set out in the examples. Suitable substrates are also taught in U.S. Pat. No. 4,113,630, supra, U.S. Pat.
No. 4,108,600 suPra, Canadian Pat. No. 1,245,533; and Canadian Pat. 1,245,943. It is advantageous to include a substrate which contains or supports the active ingredients in a premeasured, single use amount and releases them at the desired point in the wash and/or rinse cycle. The substrate may also be used to separate or compartmentalize incompatible ingredients until they are released into the wash solution. As described above, a specially designed substrate may be particularly useful to effect a sequenced delivery in which the detergent and bleach ingredients are released in the wash cycle and the soil release agent is released in the late wash and/or rinse cycle. The substrate can take almost any physical form including pouches, sheets, webs, sponges, cups, etc. It may consist of nondissolving, partially dissolving or fully dissolving material, or combinations thereof. An example of a particularly useful substrate or the present invention is a two-ply multi-pouched laminated artiole disclosed in Canadian Pat. No. 1,245,943, W.T. Bedenk and K.L. Harden.
Th2 present invention Is preferably used as part of a fully 35 formulated 5tand-alone detergent product wherein appropriate ~ detergent components are present and released along with the ~z~
peroxyacid bleach and soil release agent. Useful detergent compositions for use with this invention can include essentially any typical laundry detergent containing one or more types of organic surfactant along with detergency adjunct mat~rials. The organic ~urfactant is selected from the group consisting of anionic, nonionic, ampholytic and zwitterionic surfactants, and mixtures thereof. U.S. Pat. 3,664,961, Norris, issued May 23, 1972, describes at Col~ 1, line 68, to Col. 9, line 3, suitable surfactants useful herein. The anionic and nonionic surfactants are preferred. Nonlimiting examples of adjunctmaterials which can be used in the detergent composition include soil suspending agents, perfumes, optical ~leaches, processing aids, alkalinity sources and enzymes. Nonlimiting examples of powdered detergentmaterials suitable for use with the present invention are disclosed in U.S. Pat. No, 4,404,128, B.J. Anderson, issued Sept. 13, 1983.
Fabric softeners can also be used in combination with the components of the present invention. A pre-ferred softener is a particle formulated to survive (i.e., not dissolve in) the wash and rinse cycle, and melt and become distributed evenly on the fabric in the dryer cycle. The softener particle composition wash water survival should be at least 25%, preferably at least 40%
by weight. Numerous examples of softener/antistat compositions which function in this manner are taught in the literature, e.g., U.S. Pat. Nos. 4,113,630, Hagner et al, issued Sept. 12, 1978, and 4,108,600, supra.
A preferred fabric sotener (core) particle has the following formula:
I n~ red ient W
Ditallowdimethylammonium methylsul~ate (DTDMAMS) 4204 Sorbitan monostearate 21. 3 Cetyl alcohol 21 . 3 Bentonite clay 12 . 0 Perfume 3, 0 Total 100. 0 10The softener core particles are coated with stearyl alcohol in an amount such that the stearyl alcohol comprises 11% of the total particle composition (i.e., core plus coatingl.
The coated particles can be used "as is" as softener par-ticles with or without detergent granules. They can be over-15coated with a hard shell of ethyl cellulose, e.g., Ethocel Std. Ll, (Dow Chemical Co., Midland, Michigan 4B640). The amount of ethyl cellulose solids overcoated onto the particles is about 3% by weight of the total particle weight. The softener particles are sized through 12 on 30 Mesh U. S. Standard screens.
Deter~enttSoftener Composition A granular detergent/softener composition is prepared bymixing 3 parts of the above ethyl cellulose overcoated softener partlcles with 97 parts of the following granular detergent com-25 position.
Ing edient Wt.%
Sodium C13 linear alkylbenzene sul~onate 16.5 Sodium C1 4-C1 5 linear fatty alcohol sulfate 16 . 5 Sodium sulfate 23 . 8 Sodium silicate 9.2 Polyethylene glycol o. g Polyacrylic acid 1.3 Sodium tripolyphosphate13 . 7 Sodium carbonate 4.8 Methyl cellulose 3.6 Optical brightener 1.3 Protease enzyme 1.6 Moisture and miscellaneous 6.8 'rota I1 oo . o B leach / Softener Composition A granular bleach/softener composition is prepared by mixing 4 parts of either the above stearly alcohol coated softener par-ticles or the above ethyl cellulose overcoated softener particles with 96 parts of the following granular bleach composition.
I n~ redient Wt .
r)iperoxydodecanedloic acid 24.0 Dodecanedioic acid 2.9 Sodium C13 linear alkylbenzene su I fonate 5 . 5 Boric acid 27.7 Sodium sulfate 39.7 Miscellaneous 0. 2 Total100.0 The present invention will be further understood by the following nonlimiting examples.
E XAM PLE
A granule containing methylcellulose soil release agent which diss~lves rapidly under laundry wash cycle conditions is made according to the following procedure:
Methylcellulose powder (182 kg ~400 Ibs.) oF Dow Methocel A-15LV Premium Grade) and polyethylene glycol (182 kg (400 Ibs. ) of Union Carbide Carbowax PEG 3350) are blended in a rotating drum mixer for 5 minutes. The blended material is then divided into four 200 L (55 gal. ) fiber drums which are stored at 49C (120F) for 36 hours . The powder blend is then fed by hand into a radial extruder (Fuji Pandal Model EXDCS-100). The temperature of the material entering the extruder is ca 38C
(100F). The resulting extrudate is recycled once through the extruder. After allowing the extrudate to cool to room tempera-ture it is run through a Fitzmill Model DA506 using a U.S. No.
14 mesh screen . The resultant material is sieved on a Rotex uCing a U . S. No. 48 mesh screen to remove fine particles.
EXAMPLE l l A nonwoven fabric is coated with soil release agent according to the following procedure:
450 ml of distilled water are added to a 2000 ml stainless steel beaker and heated to 70C (158F) . 80 grams of Dow Chemical s Methocel A-15LV Premium Crade methylcellulose are slowly added to the water under good agitation conditions (a vortex was present). After the methylcellulose is well dispersed the agitation is reduced to prevent aeration. 438 grams of 20C
(68F) water are then added to the dispersion. Propylene ylycol (32.09) is then added. The beaker is then placed in an Ice bath and agitation contlnued until product became clear (an indication that the methylcellulose was dissolved). An 11.4 cm x 28 cm (4.5 in. x 11 in. ) sheet of DuPont Reemay 2420 (a spunbonded 63 g/m2 4 denier polyester fabric) was immersed in the methylcel-lulose solution. The saturated fabric was then run through an Atlas Electric Devices Co. Iaboratory wringer (Model LW-1) set at approximately 50 kg (110 Ibs. ) force. The wrung-out fabric is ~g~46~
then line dried in a low humidity environment for 24 hours.The substrate is coated with about 0.75 9 (0.028 oz.) of solid coatirlg.
EXAMPLE l l I
A bleach granule having the composition detailed below is prepared usiny the procedure described in Example I of U . S.
Pat . No. 4, 374, 035, supra .
I ng red ient Wt . %
Diperoxydodecanedioic acid24.0 Dodecanedioic acid 2.9 Sodium C13 linear alkylbenzene sul fonate 5 . 5 Boric acid 27.7 Sodium sulfate 39,7 Miscellaneous 0. 2 Total100. 0 - .
...
~g~
E)(AMPLE IV
The following granular detergent composition is prepared.
Base Granules Grams Final Composition Weight ~ Per Use Sodium C13 linear alkyl-benzene sulfonate 22.1 5.110 Sodium C1LI_15 alkyl sulfate22.1 5.110 Sodium silicate (1.6 ratio) 13.7 3.172 Sodium sulfate 32.2 7.455 Polyethylene glycol (MW = 8000) 1.5 0.340 Sodium polyacrylate lMW = 4500) 2.0 0.453 C12_13 alcohol poly-ethoxylate (6) 3.0 0.680 Sodium diethylenetriamine pentaacetate 1.5 0.34û
Moisture 2.0 0.462 23.12 Preblend Base granules 23.122 Sodium tripolyphosphate hexahydrate (powdered) 20.576 43.698 ~3i9~
EXAMPLE IV - Contd.
Admix Preblend 43. 698 Sodium tripolyphosphate (STP) hexahydrate (granular~ 19, 429 Dye 003 Brightener 0. 613 Suds suppressor prill comprising dimethylsilicone, silica, sodium tripolyphosphate and polyethylene glycol (MW = 8000) 1.703 Base Granules Crams Final Composition Weight %Per Use Protease 2 . 044 Sodium carbonate 4, 000 71, 490 Spray-On Admix 71.490 Mineral oil 0. 710 72.200 The base granules are produced by spray-drying an aqueous crutcher mix of the components on a ten foot tower using a crutcher temperature of 200F, a size 3-l/2 nozzle to make fine granules, and silicone deaeratants. I f a second drying stage on a continuous fluid bed is used to reduce moisture to 2%.
3946~
The base granules are then admixed with powdered STP
hexahydrate to form the preblend. The preblend is compacted at 50 psig roll pressure on a 4 in. by 10 in. chilsonator, and screened to select a -14(1168 microns)/+65(208 microns) particle ske cut (Tyler mesh). Oversized particles are collected and granulated on a Fitzmill, Model DA506 (The Fitzpatrick Company, Elmhurs~, Illinois 60126), using a 14 mesh screen and low rpm's.
This is screened to select a -20(833 microns)/+48(295 microns) particle size cut. Both materials are dedusted by blowing off fines in a fluid bed dryer using ambient air.
The admix is prepared as a 400 pound batch in a drum mixer. Carbonate, granular STP (with dye sprayed-on), bright-ener, enzymes, and suds suppressor prills are blended with the compacted mainstream product cut and regranulated overs at a ratio of mainstream product cut to overs of about 7 to 1. Mineral oil is sprayed on the final admix in 30 to 40 pound batches at a 19~ level using a Forberg Mixer, EXAMPLE V
A preferred mode multipouched laundry cleaning article consisting of the soil release agent coated nonwoven substrate of Example ll containing detergent tEx. IV) and bleach granular lEx. Ill) compositions is made using the following procedure. A
11.4 cm x 28 cm (4.5 in~ x 11 in.) sheet of DuPont Reemay 242û
2S la spunbonded, 63 g/rn2, 4 denier polyester fabric) Is embossecl or stretched to form a single roll of 6 cells simllar to the pattern shown in Flgs. 7 and 8 of U.S. Pat. No. 4,571,924, A.S. Bahrani, issued Feb. 25, 198fi. The six cups are em~ossed to a depth of approximately 1.0 cm (0.4 in.), and heat set. Each cup is approximately 3.6 cm. (1.4 in . ) wide and approximately 9 . 8 cm . ( 3.8 in . ) in length, each with about 30 cc capacity. Two cups are each filled with approximately 14 grams (0. 50 oz . ) of the granular bleach com-position described in Example l l l . Each of the eight cups is filled with approximately 18 grams 10.64 oz.) of the granular detergent composition described in Example IV. A topsheet ply of ~12~
the same dimensions and material as used for the embossed sheet is then attached to the filled, embossed ply by heat sealing with a sheet of polyethylene patterned to correspond to the rims of embossed ply. The nDnwoven substrate is coated with methyl-cellulose soil release agent according to Example l l such that the total level of methylcellulose in the article is about 1. lg. The AvO to soil release agent ratio for this article is about 1:1.2~ and the product delivers about 12 ppm AvO and 16 ppm of soil release agent in a 68 liter wash solution.
EXAMPLE Vl A multipouched laundry cleaning article is made according to Example V with the addition of 0.54 gram of the soil release agent granules described in Example I added to each of the four deter-gent pouches with a noncoated substrate. The total amount of soil release agent active is about 1.1 grams, thus the AvO to soil release agent ratio for this article is about 1:1.3.
.~ ,
Claims (9)
1. A laundry composition comprising effective amounts of a peroxyacid bleach and a compatible soil release agent; wherein said composition provides overall cleaning performance on hydrophobic soils on synthetic fabrics beyond that possible with a comparable amount of either said peroxyacid or said soil release agent alone; and wherein said soil release agent is selected from the group consisting of:
A. alkyl and hydroxyalkyl ethers of cellulose containing from one to four carbon atoms in the alkyl moiety and having a molar degree of substitution of about 1.5 to about 2.7 and a number average molecular weight of about 2,000 to 100,000;
B. polymers comprising ethylene terephthalate and polyethylene oxide terephthalate at mole ratio from about 1:10 to 10:1, said polyethylene oxide terephthalate containing polyethylene oxide units with a number average molecular weight from about 500 to about 10,000 and said soil release agent having a number average molecular weight of about 1,000 to 100,000:
C. polymers comprising propylene terephthalate and polyethylene oxide terephthalate at a mole ratio from about 1:10 to about 10:1, said polyethylene oxide terephthalate containing polyethylene oxide units with a number average molecular weight from about 500 to about 10,000, and said soil release agent having a number average molecular weight of about 1,000 to 100,000, or D. polymers comprising ethylene terephthalate and/or propylene terephthalate in any ratio and polyethylene oxide and/or polypropylene oxide in any ratio such that the mole ratio of ethylene terephthalate plus propylene terephthalate to polyethylene oxide plus polypropylene oxide is from about 1:10 to about 10:1, said polyethylene oxide units and said polypropylene oxide units each having a number average molecular weight from about 250 to about 10,000, and said soil release agent having a number average molecular weight of about 1,000 to about 100,000;
and mixtures thereof and wherein said peroxyacid bleach and said soil release agent are present such that the weight of available oxygen (AvO) of bleach to weight of soil release agent has a ratio of 2:1 to 1:2.
A. alkyl and hydroxyalkyl ethers of cellulose containing from one to four carbon atoms in the alkyl moiety and having a molar degree of substitution of about 1.5 to about 2.7 and a number average molecular weight of about 2,000 to 100,000;
B. polymers comprising ethylene terephthalate and polyethylene oxide terephthalate at mole ratio from about 1:10 to 10:1, said polyethylene oxide terephthalate containing polyethylene oxide units with a number average molecular weight from about 500 to about 10,000 and said soil release agent having a number average molecular weight of about 1,000 to 100,000:
C. polymers comprising propylene terephthalate and polyethylene oxide terephthalate at a mole ratio from about 1:10 to about 10:1, said polyethylene oxide terephthalate containing polyethylene oxide units with a number average molecular weight from about 500 to about 10,000, and said soil release agent having a number average molecular weight of about 1,000 to 100,000, or D. polymers comprising ethylene terephthalate and/or propylene terephthalate in any ratio and polyethylene oxide and/or polypropylene oxide in any ratio such that the mole ratio of ethylene terephthalate plus propylene terephthalate to polyethylene oxide plus polypropylene oxide is from about 1:10 to about 10:1, said polyethylene oxide units and said polypropylene oxide units each having a number average molecular weight from about 250 to about 10,000, and said soil release agent having a number average molecular weight of about 1,000 to about 100,000;
and mixtures thereof and wherein said peroxyacid bleach and said soil release agent are present such that the weight of available oxygen (AvO) of bleach to weight of soil release agent has a ratio of 2:1 to 1:2.
2. The composition of claim 1 wherein said peroxyacid bleach is selected from the group consisting of:
wherein R1 and R2 are alkylene groups containing from 1 to about 20 carbon atoms or phenylene groups, R3 is hydrogen or an alkyl, aryl, or alkaryl group containing from about 1 to 10 carbon atoms, and X and Y are selected from the group consisting of: hydrogen, halogen, alkyl, aryl, or any group which provides an anionic moiety in aqueous solution.
wherein R1 and R2 are alkylene groups containing from 1 to about 20 carbon atoms or phenylene groups, R3 is hydrogen or an alkyl, aryl, or alkaryl group containing from about 1 to 10 carbon atoms, and X and Y are selected from the group consisting of: hydrogen, halogen, alkyl, aryl, or any group which provides an anionic moiety in aqueous solution.
3. The composition of claim 1 wherein said X and Y are selected from the group consisting of:
where M is hydrogen or a water-soluble salt-forming cation.
where M is hydrogen or a water-soluble salt-forming cation.
4. The composition of claim 1 wherein said soil release agent is a methylcellulose polymer and said peroxyacid bleach is diperoxydodecanedioic acid.
5. The composition of claim 1 wherein said composition is part of a through-the-wash article, and wherein said peroxyacid bleach and said soil release agent are enclosed in a pouch made from a water-permeable, but water-insoluble, substrate material.
6. A method comprising laundering fabrics in an aqueous solution containing effective amounts of peroxyacid bleach and soil release agent according to claim 1.
7. A laundry composition comprising an effective amount of a compatible soil release agent and an organic peroxyacid bleach precursor and a peroxygen bleaching compound capable of yielding hydrogen peroxide in an aqueous solution such that an effective amount of peroxyacid is thereby generated; wherein said composition provides overall cleaning performance on hydrophobic soils on synthetic fabrics beyond that possible with a comparable amount of either said peroxyacid or said soil release agent alone: and wherein said bleach and soil release agent have a ratio of 3:1 to 1:2 on an available oxygen weight basis and wherein said soil release agent is selected from the group consisting of:
A. alkyl and hydroxyalkyl ethers of cellulose containing from one to four carbon atoms in the alkyl moiety and having a molar degree of substitution of about 1.5 to about 2.7 and a number average molecular weight of about 2,000 to 100,000;
B. polymers comprising ethylene terephthalate and polyethylene oxide terephthalate at mole ratio from about 1:10 to 10:1, said polyethylene oxide terephthalate containing polyethylene oxide units with a number average molecular weight from about 500 to about 10,000, and said soil release agent having a number average molecular weight of about 1,000 to 100,000;
C. polymers comprising propylene terephthalate and polyethylene oxide terephthalate at a mole ratio from about 1:10 to about 10:1, said polyethylene oxide terephthalate containing polyethylene oxide units with a number average molecular weight from about 500 to about 10,000, and said 50il release agent having a number average molecular weight of about 1,000 to 100,000, or D. polymers comprising ethylene terephthalate and/or propylene terephthalate in any ratio and polyethylene oxide and/or polypropylene oxide in any ratio such that the mole ratio of ethylene terephthalate plus propylene terephthalate to polyethylene oxide plus polypropylene oxide is from about 1:10 to about 10:1, said polyethylene oxide units and said polypropylene oxide units each having a number average molecular weight from about 250 to about 10,000, and said soil release agent having a number average molecular weight of about 1,000 to about 100,000;
and mixtures thereof.
A. alkyl and hydroxyalkyl ethers of cellulose containing from one to four carbon atoms in the alkyl moiety and having a molar degree of substitution of about 1.5 to about 2.7 and a number average molecular weight of about 2,000 to 100,000;
B. polymers comprising ethylene terephthalate and polyethylene oxide terephthalate at mole ratio from about 1:10 to 10:1, said polyethylene oxide terephthalate containing polyethylene oxide units with a number average molecular weight from about 500 to about 10,000, and said soil release agent having a number average molecular weight of about 1,000 to 100,000;
C. polymers comprising propylene terephthalate and polyethylene oxide terephthalate at a mole ratio from about 1:10 to about 10:1, said polyethylene oxide terephthalate containing polyethylene oxide units with a number average molecular weight from about 500 to about 10,000, and said 50il release agent having a number average molecular weight of about 1,000 to 100,000, or D. polymers comprising ethylene terephthalate and/or propylene terephthalate in any ratio and polyethylene oxide and/or polypropylene oxide in any ratio such that the mole ratio of ethylene terephthalate plus propylene terephthalate to polyethylene oxide plus polypropylene oxide is from about 1:10 to about 10:1, said polyethylene oxide units and said polypropylene oxide units each having a number average molecular weight from about 250 to about 10,000, and said soil release agent having a number average molecular weight of about 1,000 to about 100,000;
and mixtures thereof.
8. The composition of claim 7 wherein the peroxyacid-generating composition comprises:
(a) a peroxygen bleaching compound capable of yielding hydrogen peroxide in an aqueous solution; and (b) a bleach activator having the general formula:
wherein R is an alkyl containing from about 5 to about 18 carbon atoms wherein the longest linear alkyl chain extending from and including the carbonyl carbon contains from about 6 to abouk 10 carbon atoms and L is a leaving group, the conjugate acid of which has a PKa in the range of from about 6 to about 13.
(a) a peroxygen bleaching compound capable of yielding hydrogen peroxide in an aqueous solution; and (b) a bleach activator having the general formula:
wherein R is an alkyl containing from about 5 to about 18 carbon atoms wherein the longest linear alkyl chain extending from and including the carbonyl carbon contains from about 6 to abouk 10 carbon atoms and L is a leaving group, the conjugate acid of which has a PKa in the range of from about 6 to about 13.
9. A method comprising laundering fabrics in an aqueous solution containing effective amounts of a soil release agent, an organic peroxyacid bleach precursor and an inorganic peroxygen salt according to claim 7 such that an effective amount of peroxyacid is generated when dissolved in an aqueous wash solution.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/941,019 US4770666A (en) | 1986-12-12 | 1986-12-12 | Laundry composition containing peroxyacid bleach and soil release agent |
| US941,019 | 1986-12-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1299461C true CA1299461C (en) | 1992-04-28 |
Family
ID=25475805
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000554207A Expired - Fee Related CA1299461C (en) | 1986-12-12 | 1987-12-14 | Laundry composition containing peroxyacid bleach and soil release agent |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US4770666A (en) |
| EP (1) | EP0271312B1 (en) |
| JP (1) | JP2594996B2 (en) |
| KR (1) | KR960004490B1 (en) |
| AT (1) | ATE137530T1 (en) |
| AU (2) | AU623334B2 (en) |
| CA (1) | CA1299461C (en) |
| DE (1) | DE3751791T2 (en) |
| DK (1) | DK652587A (en) |
| FI (1) | FI875460A (en) |
| GR (1) | GR3019815T3 (en) |
| MX (1) | MX165827B (en) |
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-
1986
- 1986-12-12 US US06/941,019 patent/US4770666A/en not_active Expired - Lifetime
-
1987
- 1987-12-08 DE DE3751791T patent/DE3751791T2/en not_active Revoked
- 1987-12-08 EP EP87310765A patent/EP0271312B1/en not_active Revoked
- 1987-12-08 AT AT87310765T patent/ATE137530T1/en not_active IP Right Cessation
- 1987-12-11 AU AU82462/87A patent/AU623334B2/en not_active Ceased
- 1987-12-11 DK DK652587A patent/DK652587A/en not_active Application Discontinuation
- 1987-12-11 KR KR1019870014229A patent/KR960004490B1/en not_active IP Right Cessation
- 1987-12-11 MX MX009717A patent/MX165827B/en unknown
- 1987-12-11 FI FI875460A patent/FI875460A/en not_active Application Discontinuation
- 1987-12-12 JP JP62315073A patent/JP2594996B2/en not_active Expired - Lifetime
- 1987-12-14 CA CA000554207A patent/CA1299461C/en not_active Expired - Fee Related
-
1992
- 1992-02-28 AU AU11315/92A patent/AU653985B2/en not_active Ceased
-
1996
- 1996-05-02 GR GR960400960T patent/GR3019815T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DK652587A (en) | 1988-06-13 |
| EP0271312A2 (en) | 1988-06-15 |
| JPS63199296A (en) | 1988-08-17 |
| AU623334B2 (en) | 1992-05-14 |
| DE3751791T2 (en) | 1996-10-24 |
| EP0271312B1 (en) | 1996-05-01 |
| KR960004490B1 (en) | 1996-04-06 |
| ATE137530T1 (en) | 1996-05-15 |
| DE3751791D1 (en) | 1996-06-05 |
| US4770666A (en) | 1988-09-13 |
| FI875460A0 (en) | 1987-12-11 |
| AU8246287A (en) | 1988-06-16 |
| AU1131592A (en) | 1992-05-14 |
| DK652587D0 (en) | 1987-12-11 |
| AU653985B2 (en) | 1994-10-20 |
| MX165827B (en) | 1992-12-07 |
| JP2594996B2 (en) | 1997-03-26 |
| FI875460A (en) | 1988-06-13 |
| GR3019815T3 (en) | 1996-08-31 |
| EP0271312A3 (en) | 1989-10-04 |
| KR880007710A (en) | 1988-08-29 |
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